Complexes of fatty acid compounds



Patented Nov. 22, 1949 COMPLEXES OF FATTY ACID COMPOUNDS Harry M. Ullmann, Bethlehem, Pa.; Rachel Miffiin Ullmann executrix of said Harry M. Ullmann, deceased No Drawing. Application June 15, 1945, Serial No. 599,769

17 Claims. 1

The present invention relates to improved complexes between unsaturated fatty acid compounds, acyclic olefinic acids and ricinoleic materials.

It is known that adducts can be obtained between non-conjugated unsaturated nonhydroxylated fatty acids having from ten to twentyfour carbon atoms in the carbon chain, or the corresponding oils, such as linseed or olive, and acyclic olefinic acids having less than ten carbon atoms in the carbon chain, such as maleic anhydride, in accordance with the Clocker reaction. See Clocker U. S. Patents 2,188,886 and 2,275,843. The reaction takes place at temperatures in excess of 150 C. maintained for at least one-half to three-quarters of an hour, since the reaction is endothermic.

A purpose of the present invention is to plasticize such adducts of nonconjugated unsaturated nonhydroxylated fatty acids having from ten to twenty-four carbon atoms in the carbon chain, or their oils, with acyclic olefinic acids having less than ten carbon atoms in the carbon chain by forming a complex with castor oil or its fatty acid, thus producing films of increased flexibility, greater toughness and even creating rubbery characteristics.

A further purpose is to produce a speeded or a controlled gelation of the adduct as required.

A further purpose is to assist in forming filaments and monomolecular layers from the adduct.

A further purpose is to cause castor oil or its acid to dry readily.

A further purpose is to render castor oil insoluble in alcohol.

A further purpose is to increase the resistance of such adducts to the deteriorating effects of ultra violet light.

A further purpose is to increase the resistance of such adducts to rancidity.

A further purpose is to produce textile softeners by plasticizing such adducts, especially when using oils of the type of linseed in making the adducts.

A further purpose is to produce a condensation product of high index of refraction, appearing very bright in reflected light and forming films of high gloss.

A further purpose is to form esters or salts of the complexes of such adducts.

Further purposes appear in the specification and in the claims.

It has been known for some time that maleic anhydride or substances yielding maleic anhydride will react to form an adduct with nonconand similar compounds having from ten to twenty-four carbon atoms in the carbon chain. See Clocker U. S. Patents Nos. 2,188,882 to 2,188,890, inclusive and 2,275,843.

By describing the material as an adduct it is meant that the reaction occurs between an intermediate point on the carbon chain of the maleic anhydride or the like, and an intermediate point on the carbon chain of the fatty acid of the oil or similar compound.

I have discovered that definite unobvious advantages exist in forming a complex between the adduct just described and a compound having the ricinoleic acid grouping such as ricinoleic acid, its glyceride (most available as castor oil), its glycol ester, its monohydric alcohol ester (methyl, ethyl, propyl, etc.) or in fact, any mono-, dior poly-hydric alcohol ester.

The proportions of the adduct with respect to the compound having the ricinoleic acid grouping may vary widely, provided that it is recognized that with increase in the proportion of ricinoleic compound, the tendency to gel under a given heat treatment and the viscosity and drying tendency of the resulting complex will be reduced. From 5% to 500% of ricinoleic compound may be used on the weight of the adduct. The quantity of ricinoleic compound will preferably be 25% to 150% of the weight of the adduct. Typical proportions are 150%; 400%, 66% and 25% of ricinoleic compound on the weight of the adduct.

The complex is readily formed by heat treating a mixture of the adduct and the ricinoleic compound. Temperatures in excess of 70 C. and up to the temperature of decomposition of the materials may be employed. A satisfactory temperature range is 70 C. to 300 0., although C. to 230 C. is preferred and 90 C. to 130 C. is most desired. Time is important chiefly to control the degree of modification desired. At 130 C. satisfactory modification was obtained in one hour without a catalyst whereas at C. a similar modification was obtained in only five minutes using a catalyst. At 230 C. gelation was obtained in three hours, whereas at C. it took nine hours, without a catalyst in each case. It is best in each instance to heat until the desired increase in viscosity is obtained. The reaction may take place in an open vessel or a vessel equipped with a reflux condenser.

The nature of the complex is of interest. Ricinoleic acid is hydroxylated and the adduct contains acidic groups, and it therefore might be supposed that an ester is formed. Yet it is jugated unsaturated nonhydroxylated fatty oils 55 an experimental fact that the acid number, based on the adduct present, remains substantially unchanged when the complex with the ricinoleic compound forms. For example, using the 20% maleic anhydride adduct with linseed oil, and heating this adduct with 66% of castor oil at 125 C. for two hours without catalyst, a thin gel was formed after standing cold over night. Twenty-four hours later this gel had been converted on standing to a flexible rubbery solid. The acidity titration of the mixture before reacting to form the complex indicated 17.8% acid groups calculated as maleic anhydride. After the reaction the acidity titrated as 15.3%. The difference is obviously insufficient to account for ester formation.

In general, repeating this experiment with varying proportions of adduct to ricinoleic compound, the acidity remaining after formation of the complex corresponds within the experimental error to the quantity of adduct which was present before the reaction.

There are of course double bonds present, and it might be supposed that the complex has resulted from a combination of double bonds. On

the other hand, the iodine member after formation of the complex is unchanged.

The 20% maleic anhydride adduct of linseed oil alone (without ricinoleic compound, such as castor oil) was heated on the steam bath with 1.5% catalyst (toluene sulphonic acid) for five hours and fifteen minutes. There was slight thickening, but the oil flowed freely at room temperature. After one month of exposure to the air, the adduct formed a skin, but the remaining oil flowed freely when the skin was broken. On the other hand, when the experiment was re peated adding castor oil to the adduct the product gelled at 83 C. in a few minutes and remained gelled at 97 C.

It would appear likely that the reaction is one of united action and not a conventional esterification or saturation. The properties imparted are interesting and not of the character which would be expected. 1

Notwithstanding that unmodified castor oil does not readily gel by itself, the castor oil speeds the gelation of the adduct. At the same time it increases the flexibility of the film or mass formed, increasing the toughness and adding rubbery characteristics. Although castor oil does not dry, the complex has good drying properties. Unlike castor oil, the complex is not soluble in ethyl alcohol, the complex has good properties in forming filaments and mono-molecular layers.

The ricinoleic grouping imparted by complex formation greatly increases the resistance of the adduct to ultra violet light.

The resistance of the adduct to rancidity is also greatly improved by forming the ricinoleic complex of the present invention. This aids in storage as well as assisting when the product of the invention functions in textile softeners.

For textile softeners, it is possible to use comparatively inexpensive adducts, such as the linseed oil-maleic anhydride adduct, and still obtain adequate plasticity, due to the ricinoleic complex.

A valuable property imparted by the ricinoleic rouping is high refractive index, making the film appear very bright in reflected light. This is useful in paint films of high gloss.

It is expected that the usefulness of the complex will be primarily in the coating and plastic or elastomer field. Under coatings it has value for paint, varnish, lacquer and enamel vehicle and resin constituents, linoleums, oil cloths, polishes and patent leathers. textile finishes. The rubbery character is valuable as an elastomer or synthetic rubber or plastic.

FORMATION OF ADDUCTS known in the art (Bernsthen, Textbook of Organic Chemistry (1923) pages 250 to 256).

Instead of maleic anhydride, an acid ester of maleic acid, or a substituted maleic acid having less than ten carbon atoms in the carbon chain, may be used.

Whenever reference is made herein to maleic anhydride it will be understood that I include substances which yield maleic anhydride if subjected to the conditions under which maleic anhydride is produced. I also include substituted maleic acids having less than ten carbon atoms in their carbon chains, and other equivalents.

Whenever I refer herein to an acid or an acid group, I of course include an acid anhydride and an acid anhydride group, and vice versa. Whenever I refer to an ester, I include also a half ester.

Investigation of a large number of compounds has shown that the ability to form adducts of the types herein referred to its characteristic of chain compounds having the ethylene linkage and having less than ten carbon atoms in the carbon chains, which are substituted'on one or both sides of the double band to form acids or acid anhydrides, or half esters thereof or similar compounds. These compounds are olefinic as they are acyclic and have the ethylene linkage. Such olefinic compounds are mono-substituted when they have only one acidic group; for example crotonic acid. Such olefinic compounds are di-substituted when they contain two acidic groups; for example, maleic anhydride, citraconic anhydride, maleic acid, acid methyl maleate.

The longer the carbon chain of the acyclic olefinic acid or acid anhydride, or half ester thereof, the less vigorous is the condensation reaction. Thus at the upper limit (nine carbon atoms in the carbon chain) the reaction is relatively mild. If there are less than seven carbon atoms in the carbon chain (for example six) the reaction is more vigorous. A still more vigorous reaction is obtained if there are less than five carbon atoms in the carbon chain. In the case of any ester of any olefinic compound, the carbon chain of the olefinic compound should have less than ten carbon atoms, the carbon chain of the compound added by esterfication not being counted.

In all cases where I refer to less than ten carbon atoms in all the carbon chain of the acyclic olefinic compound, it will be understood that a more vigorous reaction will be obtained with compounds having less than seven carbon atoms in the carbon chain, and a still more vigorous reaction with compounds having less than five carbon atoms in the carbon chain. These latter are to be included, whenever mention is made of less than ten carbon atoms in the carbon chain.

For making the adduct, a wide variety of non- It offers promise for conjugated unsaturated nonhydroxylated carbon chain compounds having from ten to'twenty fourcarbon atoms in the carbon chain may be used. Esters of fatty acids with mono-, di-,. or polyhydric' alcohols, for example, glyceryl or ethylene glycol esters, are very desirable.

Where reference is made to the length of the carbon chain as being from ten to twenty-four carbon atoms, it is intended to include compounds having ten carbon atoms, twenty-four carbon atoms, or any intermediate number of carbon atoms in the chain. The reference to the length of the carbon chain refers to the carbon chain of the acid. The glyceride, for example, contains three such carbon chains united. to a glyceryl group.

As examples of the type of nonconjugated unsaturated nonhydroxylated aliphatic acids having from ten to twenty-four carbon atoms in the carbon chain, whose esters I may use, I suggest oleic, linoleic, linolenic, clupanodonic and undecylenic. The esters of the nonhydroxylated fatty acids may be glyceryl esters, in which case they will be oils such as corn, olive, cotton seed, peanut, linseed, sunflower, safflower, perilla, hemp seed, walnut seed, soya bean, rape seed, tomato seed, neats foot, lard, codliver, cod, burbet, salmon, menhaden and many others. Esters of other alcohols, such as ethylene glycol esters may be used. It will also be understood that esters" of mixtures of various fatty acids, or mixtures of esters, or mixtures of esters and fatty acids, may be employed.

The oils just referred to may generally be described as oils predominantly consisting of glycerides of linoleic and cello acids.

When I refer to the grouping of a nonconjugated unsaturated nonhydroxylated aliphatic acid having from ten to twenty-four carbon atoms in the carbon chain, I mean to include the esters of the acid, whether with monodi-, or polyhydric alcohols.

In forming the adduct, I may desirably employ one molecular equivalent of nonco-njugated unsaturated nonhydroxylated aliphatic ester or the like to one molecular equivalent of acyclic olefi-nic acid and subject the mixture to a temperature of between 150 C. and 300 C. (more desirably between 180 C. and 260 C.) and preferably also to high pressure to facilitate the reaction. The temperature may in some cases be considerably in excess of 300 C. if the reacting components can stand such high temperatures. The reaction will desirably proceed for a time of at least one-half to three-quarters of an hour, and sufficient to produce substantial condensation. Very good results are obtained using temperatures of at least 150 C. and in excess of the ordinary boiling point: of the acyclic olefinic acid with return condensation. Pressure may desirably be applied by simply confining the reacting components between the Walls of some vessel such as a pressure autoclave and then heating the reaction components.

Pressure may also be applied in any other suitable way, as by pumping the reaction components into the vessel or introducing an inert gas under pressure. Pressures up to 300 pounds per square inch have been used with success. Of course, the desirable pressure will vary with the individual reaction.

A suitable catalyst may be used to accelerate the reaction and to increase the yield. It is. not, however, usually necessary to use a. catalvs The formation of the adduct may occur in thepresence: of. suitable solvents, although. this is not usually necessary.

In ordinary practice it is preferred not to use enough acyclic olefinic acid having less than ten carbon atoms in the carbon chain, to saturate all the double bonds in the fatty oil, etc. havingv from ten to twenty-four carbon. atoms. in. the carbonchain. The adduct thus ordinarily has aniodine value.- Generally it is sufficient to saturate one-sixth to one-third of the double bonds in the fatty oil etc. Thus in. olive. oil one-third. of the double bonds (one) is ordinarily saturated, and in linseed oil one-sixth (one). But in individualcases it may be desirable: to saturate more ethylene. linkages in. the fatty oil, or even to saturate them. completely. To saturate all of the double bonds in linseed oil, six molecular equiva- Lents of the acyclic olefinic acid having less than. ten carbon. atoms in the carbon. chain are caused to react withone molecular equivalent of linseed oil.

Example 1 In a pressure autoclave, 180 parts by weight of alkali refined linseed oil are mixed with twentyparts by weight of maleic anhydride. The temperature is maintained at from 230 C to 260 C. for one hour, a pressure of about thirty pounds per square inch developing. The reaction may be obtained satisfactorily at C., but is much slower at this low temperature, and. the temperature may be raised to 300 C. or even somewhat higher; but a high temperature may cause some diiiiculty due to carbonization. After cooling the reaction product is removed from the autoclave. The adduct is slightly darker and more viscous than the original linseed oil. It is soluble in acetone, ethyl acetate, ether, xylene, carbon tetrachloride, higher petroleum hydrocarbons and turpentine, and semi-soluble in 95% ethyl alcohol. The adduct is miscible with fatty oils, and solutions of cellulose derivations such as nitrocellulose in all proportions. The iodine value is 141.4, as against 190.0 for the original linseed oil. The saponification value is 288 and the acid value is 52.9 in the presence of ethyl alcohol.

Example 2 To parts by weight of linseed oil are added 25 parts by weight. of citraconic anhydride (an alkyl. substituted maleic anhydride) and the mixturezis heated in a: three-neck flask, equipped with a. reflux condenser, at about 250 C; for about three-quarters of an hour. At the end of this period no further citraconicanhydride appears to condense under the reflux, indicating completion of the adduct. As a precaution, heating is continued about 15 minutes longer. This adduct is less viscous than the maleic adduct of linseed oil obtained in Example I, but is otherwise similar.

Example 3 A mixture of 25 parts by weight of linseed oil and 2.4 parts by weight of crotonic acid (an acyclic olefinic acid) are heated under pressure at about 250 C. for about two hours. The properties of the adduct are very similar to those obtained fromthe maleic linseed oil adduct of Example 1.

Example 4 A mixture of 900 partsbyweight of linseed oil and 112 parts by weight of acid methyl maleate (a. maleic half ester) is heated under pressure at about-250 C. for about two hours. The adduct,

Iii although less acidic than the: adducts' obtained.

in Examples 1 to 3, may nevertheless be reacted later in a manner explained below.

Example 5 A mixture of 100 parts by weight of olive oil and 20 parts by weight of maleic anhydride is heated in a flask equipped with a reflux condenser at 200 C. for one hour. A product similar to Example 1, but not drying readily, is obtained.

The adduct may be made with nonconjugated unsaturated nonhydroxylated drying, semi-drying or non-drying fatty oils having from ten to twenty-four carbon atoms in the carbon chain, or mixtures of the same, and the characteristics of the adduct are to some extent dependent upon the character of the oils or the like employed in the reaction. For convenience the group of semidrying oils is classified with the group of drying oils. When nonconjugated unsaturated nonhydroxylated drying oils are caused to react with maleic anhydride or the like, the products dry in th air at ordinary temperatures to form hard dry films, whether or not dryers are used. These same adducts generally exhibit thermo-hardening properties, being convertible at '70 to 80 C. for example, into hard resistant varnish-like films in short periods of time. When maleic anhydride or similar adducts of nonconjugated unsaturated nonhydroxylated semi-drying oils such as sunflower, soya or safllower are used, drying does not occur so readily as with the drying oils. An example of the drying behavior of the adducts is as follows:

Example 6 A 1:1 xylene solution of the adduct of Example 1 to which soluble driers are added to the extent of 0.03% of cobalt, 0.05% of manganese and 0.5% of lead, for example in the form of linoleates and resinates, dries to a hard film at room temperature in about one and one-half hours. The film produced is not acted upon by water, ethyl alcohol, benzine or xylene.

In making the adduct, the quantity of acyclic olefinic acid or the like will ordinarily be from 2 to 30% of the nonconjugated unsaturated nonhydroxylated fatty acid or oil. The reaction in forming the adduct is usually considered to be complete when less than 0.3% of unreacted acyclic olefinic acid remains based on the weight of nonconjugated unsaturated nonhydroxylated fatty acid or oil, although it may not be necessary in every case to carry the adduct formation to that extent of completeness.

COIVIPLEX In producing the complex, very pronounced differences can be obtained by changing the proportions of ricinoleic compound to adduct, as well as the composition of the adduct. This will be clear from the following examples:

Example 7 The 20% maleic anhydride adduct of linseed oil was heated on the steam bath with 25% castor oil on the weight of the adduct. Catalyst was included (toluene sulphonic acid) in the proportion of 1% of the total reacting ingredients. After 45 minutes the mass had formed. a resilient gel at steam bath temperature.

Example 8 The 20% maleic anhydride adduct of linseed oil was heated on the steam bath at 97 C. with 25% of castor oil on the weight of adduct and 0.5% of toluene sulphonic acid catalyst. The

complex, cooled after 30 minutes, was spread as a film, after adding cobalt naphthenate drier. The film dried in 24 hours without drag into a hard, firm, light colored layer.

As the percentage of ricinoleio compound is increased, the tendency to gel is reduced, and the product after a given treatment may be somewhat thinner.

Example 9 The 10% maleic anhydride adduct of linseed oil was heated with 33% of castor oil on the weight of the adduct. Toluene sulphonic acid catalyst was included to the extent of 1% of the total. The temperature of 97 C. was maintained for 4 hours. The complex had a Gardner-Holdt number between Z5 and Z6, but was of light color.

In the presence of cobalt naphthenat drier the complex dried in air to a slight drag in 15 hours and dried in air without drag as a hard firm film in 21 hours.

Two influences tend to reduce the gelation in Example 8 as compared with Example 7. One is the larger proportion of ricinoleic compound and the other is the smaller proportion of maleic anhydride in the adduct.

Example 10 A mixture of the 10% maleic anhydride adduct of linseed oil with 33% of castor oil was heated on the steam bath at 98 without catalyst for 11.5 hours. The complex was highly viscous, suitable for artificial leather coatings or for patent leather.

On treating compositions having higher ricinoleic compound content, the tendency to gel is less pronounced, but gelation may be obtained at higher reaction temperatures.

Example 11 The 10% maleic anhydride adduct of castor oil was heated in an open fiask with 66% of castor oil on the weight of the adduct, in the absence of the catalyst and for a time of three hours. Incipient gelation resulted, and after cooling to room temperature the product gelled hard in one day. The resinous complex was quite light in color.

Example 12 Using the same ingredients and proportions as Example 11, the heating was conducted on the steam bath at 97 C. After three hours the Gardner-Holdt viscosity of the complex was Z6 while after five hours it was greater than Z6. The viscous complex was soluble in ammonium hydroxide and sodium hydroxide aqueous solutions, due to salt formation at the acidic group.

Erample 13 The 20% maleic anhydride adduct of linseed oil was heated with castor oil in the proportion of 66% of the weight of the adduct, and 0.1% of the total as toluene sulphonic acid catalyst. The temperature was between and C. fo 15 minutes, then between 85 and 99 C. for 25 minutes and at 99 C. for 50 minutes after cooling to room temperature the complex flowed slowly. After standing at room temperature for one month, it gelled solid. When this example was repeated heating at 85 C. for 35 minutes, a heavy complex liquid was formed which gelled after two weeks at room temperature to a tough elastic rubbery mass.

Example 14 Using the same ingredients and proportions .as Example 13, but with 1.5% toluene sulphonic acid catalyst, heating in an open flask at 78 to 85 C. for 30 minutes, the complex was very thick at reaction temperature and gelled completely on cooling to room temperature to a tough rubbery mass.

Example 1.5

Equal weights of the 20% maleic anhydride adduct of linseed oil and of castor oil were heated at 97 C. on the steam bath in the absence of alyst. The Gardner-Holdt viscosities ran as follows:

Time Elapsed $31K;

'Z3 Z6 Z6 gel Gelling is favored by using an adduct whose content of maleic anhydride is higher.

Example 16 Equal weights of the 30% maleic anhydride adduct of linseed oil (made by heating in a flask equipped with a reflux condenser for 40 minutes at about 230 C.) and castor oil were heated with 0.5% toluene sulphonic acid catalyst on the total weight over the steam bath. Samples heated 15 and 30 minutes both gelled hot. The 15 minute product flowed slowly hot, but was rubbery when cold. The 30 minute product could not be made to flow hot or cold.

Example 17 Example 18 The 20% maleic anhydride adduct .of linseed oil was heated at 97 C. over the steam bath with 30% of castor oil on the weight .of the adduct and 1% of toluene sulphonic acid on the weightof the total. After two hours heating the complex was dissolved in ether, cobalt .naphthenate drier added, and the solution applied to a glass plate. After 18 hours a slight tack remained on the film. After 24 hours the film was dry without drag.

Example 19 The 20% maleic anhydride adduct of linseed oil was heated on the steam bath at about 97 .C. with 400% of castor oil, based on the weight of the adduct, and 1.0% of toluene sulphonic acid catalyst. After 18 hours of heating the complex was thickened. The reason for the .long heating time is the preponderance .of castor oil.

Example 20 The 20% maleic anhydride adduct of olive oil (a typical non-drying oil) was made by heating at 230 C. for about one hour with return condensation. The Gardner-Holdt viscosity number of the adduct was V or 8.84 poises. This adduct when heated at 97 C. for 55 minutes with one percent of toluene sulphonic acid increased its Gardner-Holdt viscosity number only to X or 12.9 poises. On the other hand, when this adduct was heated for 45 minutes at 97 C. with an equal quantity of castor oil and 1% of toluene sulphonic acid on the weight of the mixture, the Gardner-Holdt viscosity number was beyond Z6 and thus far beyond the Gardner-Holdt range. A bubble trapped in the complex does not ascend in several days. The product has many filmforming properties similar to the linseed oil complex.

While the catalyst is preferably toluene sulphonic acid, any sulphonic acid such as camphor sulphonic acid, benzene sulphonic acid or the like may be used. In fact any organic acid carrying S03 in soluble form into the reaction ingredients may be used.

The quantity of catalyst may be desirably 0.1 to 1.5%, 1% being very successful, based on the total weight of reactants. The quantity of catalyst, if high, merely may discolor the product. With a catalyst it is possible to obtain a distinct increase in viscosity at 85 C. by heating only five minutes, and to gel in 15 minutes. Of course, with longer heating, the result can be obtained without using any catalyst.

The speed of reaction is of course lowered by the increase in the proportion of ricinoleic compound and reduction in the maleic anhydride content in the adduct. Without catalyst at steam bath temperatures, 10 hours may be required for gelation. At 230 C. however, gel can be formed withoutcatalyst in about 3 hours.

The complex still has acidic groups practically unimpaired. These will react with alkalis or substituted alkalis like sodium, potassium, lithium, or ammonium hydroxide or quaternary ammonium hydroxide (tetra methyl ammonium hydroxide, trimethyl ethyl ammonium hydroxide or tetra ethyl ammonium hydroxide) or an amine (triethylamine, trimethylamine, diethylmethylamine) to form water soluble oils useful in water paints. The complexes will also esterify with mono-, dior polyhydric alcohols to produce compounds useful as plasticizers, softeners and textile finishes. Suitable alcohols are methyl, ethyl, propyl, isopropyl, butyl, etc., ethylene glycol, glycerol, and pentaerythritol.

The product of the invention is very desirable for a number of uses, not only because of its good film forming properties, including resilience, but also because of its excellent drying characteristics, resilience, index of refraction and low tendency to rancidity.

In view of my invention and disclosure, variations and modifications to meet individual whim or particular need will doubtless become evident to others skilled in the art, to obtain all or part of the benefits .to my invention without copying the product or process shown, and ,I, therefore, claim all such insofar as they fall within the reasonable spirit .and scope of my claims.

Having thus described my invention what I claim as new and desire to secure by Letters Patent is:

'1. The process of forming a complex, which comprises reacting a compound containing a nonconjugated unsaturated nonhydroxylated fatty acid grouping having from ten to twentyfour carbon atoms in its carbon chain at the carbon chain with an acyclic .olefinic acid having less than ten carbon atoms .in its carbon chain and then heating the adduct thus produced at a 11 temperature of between 70 and 130 C. with a compound of the group consisting of recinoleic acid and its completed esters to form a complex.

2. The process of forming a complex, which comprises reacting a compound containing a nonconjugated unsaturated nonhydroxylated fatty acid grouping having from ten to twentyfour carbon atoms in its carbon chain at a temperature in excess of 150 C. and for a time of at least one-half hour with from 2 to 30% of an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, and then heating the adduct thus produced at a temperature of between 70 and 130 C. with from 5 to 500% of a compound of the group consisting of ricinoleic acid and its completed esters.

3. The process of forming a complex, which comprises reacting a compound having a nonconjugated unsaturated nonhydroxylated fatty acid grouping with from ten to twenty-four carbon atoms in its carbon chain at the carbon chain with from 2 to 30% of maleic anhydride and then heating the adduct thus formed at a temperature of between 70 and 130 C. with from 25 to 150% of a compound of the group consisting ricinoleic acid and its completed esters.

4. The process of forming a complex, which comprises reacting a compound having a nonconjugated unsaturated nonhydroxylated fatty acid grouping with from ten to twenty-four carbon atoms in its carbon chain at the carbon chain with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain and then heating the adduct thus produced at a temperature between 70 and 130 C. with from 5 to 500% of castor oil until the viscosity is substantially increased.

5. The process of forming a complex, which comprises reacting linseed oil with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain at a temperature of between 150 and 300 C. for at least one-half hour and then heating the adduct thus produced with castor oil at a temperature of between 70 and 130 C. until the viscosity is substantially increased.

6. The process of forming a complex, which comprises reacting olive oil with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain at a temperature of between 150 and 500 C. for at least one-half hour and then heating the adduct thus produced with castor oil at a temperature of between 70 and 130 C. until the viscosity is substantially increased.

7. The process of forming a complex, which comprises reacting a compound containing a nonconjugated unsaturated nonhydroxylated fatty acid grouping having from ten to twentyfour carbon atoms in the carbon chain at a temperature in excess of 150 C. with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain for a time of at least one-half hour and then heating the adduct thus produced at a temperature of from 70 to 130 C. with from 5 to 500% of a compound of the group consisting of ricinoleic acid and its completed esters in the presence of a sulphonic acid catalyst.

8. The process of controlling the viscosity or gelation of an adduct, which comprises heating the adduct of a nonconjugated unsaturated nonhydroxylated fatty oil having from ten to twenty-four carbon atoms in the carbon chain of its fatty acid combined at its carbon chain with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, with a selected 12 quantity of castor oil between 5 and 500% of the weight of the adduct at a temperature of between 70 and C. for a controlled time.

9. The process of forming a complex, which comprises reacting a compound containing a nonconjugated unsaturated nonhydroxylated fatty acid grouping having from ten to twentyfour carbon atoms in its carbon chain at the carbon chain with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, then heating the adduct thus produced at a temperature of between 70 and 130 C. with a compound of the group consisting of ricinoleic acid and its completed esters to form a complex, and neutralizing acidic groups in the complex.

10. A complex having an adduct containing a nonconiugated unsaturated nonhydroxylated fatty acid grouping having from ten to twentyfour carbon atoms in its carbon chain combined at its carbon chain to an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, having a compound of the group consisting of ricinoleic acid and its completed esters, and having an acidity of the complex substantially the same as the acidity of the adduct plus the acidity, if any, of the compound of the group unreacted.

11. A complex having an adduct containing a nonconjugated unsaturated nonhydroxylated fatty acid grouping having from ten to twentyfour carbon atoms in its carbon chain combined at its carbon chain with from 2 to 30% on the weight of the aforesaid of an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, having from 5 to 500% on the weight of the adduct of a compound of the group consisting of ricinoleic acid and its completed esters, and having an acidity of the complex substantially the same as the acidity of the adduct plus the acidity, if any, of the compound of the group unreacted.

12. A complex having an adduct containing a nonconjugated unsaturated nonhydroxylated fatty oil having from ten to twenty-four carbon atoms in the carbon chain of its fatty acid combined at its carbon chain to an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, having a compound of the group consisting of ricinoleic acid and its completed esters, and having an acidity of the complex substantially the same as the acidity of the adduct plus the acidity, if any, of the compound of the group unreacted.

13. A complex having linseed oil combined at its carbon chain with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, having a compound of the group consisting of ricinoleic acid and its completed esters, and having an acidity of the complex substantially the same as the acidity of the adduct plus the acidity, if any, of the compound of the group unreacted.

14. A complex having olive oil combined at its carbon chain with an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, having a compound of the group consisting of ricinoleic acid and its completed esters, and hav ing an acidity of the complex substantially the same as the acidity of the adduct plus the acidity, if any, of the compound of the group unreacted.

15. A complex having an adduct containing a nonconjugated unsaturated fatty acid grouping with from ten to twenty-four carbon atoms in its carbon chain combined at its carbon chain to from 2 to 30% of maleic anhydride, having 13 from 5 to 500% on the Weight of the adduct of a compound of the group consisting of ricinoleic acid and its completed esters, and having an acidity of the complex substantially the same as the acidity of the adduct plus the acidity, if any, of the compound of the group unreacted.

16. A complex having an adduct containing a nonconjugated unsaturated fatty acid grouping with from ten to twenty-four carbon atoms in its carbon chain combined at its carbon chain to from 2 to 30% of maleic anhydride, having from 5 to 500% on the weight of the adduct of castor oil, and having an acidity of the complex substantially the same as the acidity of the adduct plus the acidity, if any, of the compound of the group unreacted.

17. A Water soluble product consisting of the neutralization product of a complex having an adduct containing a nonconjugated unsaturated nonhydroxylated fatty acid grouping having from 14 ten to twenty-four carbon atoms in its carbon chain combined at its carbon chain to an acyclic olefinic acid having less than ten carbon atoms in its carbon chain, having a compound of the group consisting of ricinoleic acid and its completed esters, and having an acidity of the complex before neutralization substantially the same as the acidity of the adduct plus the acidity, if any of the compound of the group unreacted.

HARRY M. ULLMANN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,275,843 Clocker Mar. 10, 1942 2,306,281 Rust Dec. 22, 1942 Wayne May 4, 1943 

